Micronutrient compositions and systems and methods of using same

ABSTRACT

An agricultural spray may be produced by admixing citric acid and glutamic acid with a metal salt and a pesticide or other agricultural chemical containing components capable of precipitating with the metal salt in the admixture. The citric acid and the glutamic acid chelate with the metal salt to provide a stability and compatibility-enhancing composition, thereby preventing the metal salt from forming an insoluble solid within the admixture. Such a composition may be produced by admixing citric acid and glutamic acid at a molar ratio of about 6.8:0.5 to about 1:0.29. The composition may include a metal sat, citric acid and glutamic acid in a molar ratio of about 1:6.8:0.5 to about 1:1:0.29 and a pesticide.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a continuation of U.S. Ser. No. 16/221,018, filedDec. 14, 2018, now U.S. Pat No. 10,464,856, which is a continuation ofU.S. Ser. No. 15/874,447 filed on Jan. 18, 2018, now U.S. Pat. No.10,167,238, which is a continuation of U.S. Ser. No. 14/868,982 filedSep. 29, 2015, now U.S. Pat. No. 9,908,821. Each of the foregoingapplications is incorporated herein, in its entirety, by this reference.

TECHNICAL FIELD

The present disclosure relates to products, systems and methods forusing compositions for improving the stability and compatibility ofagricultural products, and more particularly, for improving thestability and the compatibility of micronutrients in agriculturalmixtures.

BACKGROUND

Crop protection involves application of herbicides, insecticides,fungicides, collectively known as pesticides, to control the growth ofweeds, harmful insects and plant diseases that afflict crops. Withoutthese practices, food production would decline, many fruits andvegetables would be in short supply, and the price of food would rise.Further, fibers for textile manufacturing, such as cotton, woulddecrease as farmers would lose their harvests due to pests and diseases.

Pesticides are typically applied in combination with adjuvants toimprove pesticide performance. Adjuvants are substances in a pesticideformulation or added to the spray tank to improve pesticidal activity orapplication characteristics. In addition, micronutrients may be appliedin combination with pesticides and adjuvants. Micronutrients includeselements essential for plant growth and include boron (B), copper (Cu),iron (Fe), chloride (Cl), manganese (Mn), molybdenum (Mo) and zinc (Zn).For instance, boron assists plants in use and regulation of othernutrients, aids production of sugar and carbohydrates, and is requiredfor seed and fruit development. Copper is important for reproductivegrowth, aids in root metabolism and helps in the utilization ofproteins. Chloride aids plant metabolism. Iron is a necessarymicronutrient in the formation of chlorophyll. Manganese is used byplant enzyme systems and is involved in the breakdown of carbohydrates,as well as nitrogen metabolism. Molybdenum assists in the use ofnitrogen. Zinc is needed by the plant for regulating plant growth and incarbohydrate and sugar metabolism. While some micronutrients are foundin soil, others are not; and some soil-based micronutrients may not beat levels sufficient for plant growth.

However, many pesticides contain phosphate salts that bind to the metalions of the micronutrient and convert them to insoluble solids beforethe micronutrient can be absorbed by the plant, rendering micronutrientineffective. In prior approaches, ethylenediaminetetraacetic acid (EDTA)has been used as a chelating compound that operates to bind metal ionsof the micronutrient and prevents phosphate salt from converting themicronutrients to insoluble solids. While EDTA prevents phosphate frombinding to metal ions, the metal ions exhibit diminished reactivity. Inaddition, EDTA is not accepted for use as a chelator in all countries.Other chelating compounds include organic acids and amino acids such asthose described in U.S. Pat. No. 5,504,055 and US Patent ApplicationPublication 2005/239673, which are incorporated herein for any purpose.

SUMMARY

Implementations provide compositions for use with agricultural chemicalscontaining components capable of precipitating with micronutrients(e.g., metal salts), and approaches for using these compositions.

According to certain implementations, a method of spraying anagricultural spray involves admixing a composition comprising citricacid and glutamic acid with a metal salt and a pesticide, the pesticidecomprising phosphate, where the citric acid and the glutamic acidchelate with the metal salt to thereby prevent the metal salt fromforming an insoluble solid with the phosphate.

In various implementations and alternatives, the citric acid and theglutamic acid are present in the composition at a molar ratio of about6.8:0.5 to about 1:0.29; the metal salt is present with the citric acidand the glutamic acid at a molar ratio of about 1:6.8:0.5 to about1:1:0.29; the metal salt is a metal salt of one or more of zinc, boron,copper, iron, chloride, manganese, molybdenum, cobalt, magnesium,calcium or nickel; the metal salt is a metal oxide; metal oxide is zincoxide; the pesticide includes N-(phosphonomethyl)glycine and/or one ormore of a salt, an ester or a derivative thereof.

According to another implementation, a method of producing a compositioninvolves admixing a composition comprising citric acid and glutamic acidat a molar ratio of about 6.8:0.5 to about 1:0.29.

In various implementations and alternatives, the method further involvesproducing a chelated composition by mixing the composition with a metalsalt, where the molar ratio of the chelated composition of the metalsalt, the citric acid and the glutamic acid may be about 1:6.8:0.5 toabout 1:1:0.29; producing an agricultural spray by mixing the chelatedcomposition with a pesticide or a fertilizer. Such pesticides mayinclude one or more of: N-(phosphonomethyl)glycine,4-Dichlorophenoxyacetic acid, bentazon, 3,6-dichloro-o-anisic acid,3,6-dichloro-2-methoxybenzoic acid,1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine, amide herbicides,arsenical herbicides, carbamate and thiocarbamate herbicides, carboxylicacid herbicides, dinitroaniline herbicides, heterocyclicnitrogen-containing herbicides, organophosphate compounds, ureaherbicides, quaternary herbicides,5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamide;tembotrione or derivatives thereof.

According to yet another implementation, an admixture of a compositionincludes a metal salt, citric acid and glutamic acid in a molar ratio ofabout 1:6.8:0.5 to about 1:1:0.29 and a pesticide.

In various implementations and alternatives, the metal salt is a metalsalt of one or more of zinc, boron, copper, iron, chloride, manganese,molybdenum, cobalt, magnesium, calcium or nickel; the metal salt is ametal oxide such as zinc oxide; and the pesticide may include any of theaforementioned pesticides alone or in combination.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a photograph of a composition disclosed in the prior art.

FIG. 1B (left) is a photograph of a chelated composition of the presentdisclosure and (right) of the composition disclosed in the prior art.

DETAILED DESCRIPTION

Overview: Compositions of the present disclosure contain organic acidsand amino acids at a ratio that binds (e.g., chelates) metal ions of themicronutrient to prevent salts (e.g. phosphate salts) commonly found inagricultural chemicals from converting the micronutrients to insolublesolids, while at the same time, prevents fouling of agricultural sprayequipment or of pesticides. The compositions, accordingly, providestability and compatibility for micronutrients in pesticides.

Metal ions commonly used in connection with the stability andcompatibility-enhancing compositions include period 4 transition metals.These transition metals include, but are not limited to: V, Cr, Mn, Fe,Co, Ni, Cu, and Zn. Period 4 transition metals include six chelationsites. The disclosed compositions include coordination sites forchelating with such transition metals. For instance, citric acid hasthree coordination sites for chelation and glutamic acid has fourchelation sites.

While prior approaches have used citric acid as a chelating agent thatbinds to metal ions, it has been discovered that the use of citric acidchelating agents results in problems when mixed with agricultural sprays(such as orthophosphate-based fertilizers including 9-18-9 fertilizers(i.e., 9% nitrogen-18% phosphate-9% potassium) and 7-23-5 fertilizers).For instance when used with glyphosate, e.g., Durango DMA, the citricacid is incompatible with the glyphosate and causes the precipitation ofsalts, which block screens and spray tips in agricultural sprayapplications. When used with, 2,4-Dichlorophenoxyacetic acid (2,4-D) andglyphosate, e.g., Enlist Duo, the citric acid results in breaking theemulsion. Further, some products that contain micronutrients that arenot chelated are problematic when mixed with agricultural sprays. Forinstance, when micronutrients such as boron, zinc and manganese aremixed with glyphosate in its various forms (e.g., salts of glyphosate)as well as Basagran, amide herbicide nitro-phenol ethers including5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamide(e.g., Fomesafen), and orthophosphate-based fertilizers (e.g., 9-18-9and 7-23-5 fertilizers), the combination results in precipitation of themetal ion. In another example, when micronutrients are combined withglyphosate in combination with other pesticides such as2,4-Dichlorophenoxyacetic acid (2,4-D) (e.g., Enlist Duo), the result isa combination of precipitation of the metal ion and breaking theemulsion.

Description of the Embodiments: It has been discovered that thecombination of citric acid in combination with glutamic acid at a molarratio of about 1:0.29 to about 6.8:0.5 (where citric acid contains 192.1g/mol, and glutamic acid contains 147.1 g/mol) provides a stability andcompatibility-enhancing composition that is effective at preventingmicronutrients from reacting with phosphate salts in agriculturalcompositions such as pesticides and fertilizers, while at the same timeprevents fouling of agricultural spray equipment or of pesticides. Inparticular implementations, the composition may include a citricacid:glutamic acid molar ratio of about 14:1, 13:1, 12:1, 10:1, 9:1,8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or 1:1. In some implementations, thepreferred citric acid:glutamic acid molar ratios may be about 2:1 or0.9:0.5.

The disclosed compositions may be used in, or may include, a variety ofmicronutrients in the form of metal ions including water soluble saltsof zinc, boron, copper, iron, chloride, manganese, molybdenum, cobalt,magnesium, calcium, and nickel or mixtures thereof. For instance, themetal salts may include the water soluble salts, sulfates, nitrates,hydroxides, acetates, carbonates, chlorides, phosphates or mixturesthereof. In some implementations, the preferred metal salts includeszinc salts such as zinc sulfate (ZnSO₄), zinc nitrate (Zn(NO₃)₂), zincoxide (ZnO), zinc chloride (ZnCl₂), zinc chlorate Zn(ClO₃)₂, zincphosphate (Zn₃(PO₄)₂), zinc molybdate (ZnMoO₄), zinc chromate (ZnCrO₄),zinc fluoride (ZnF₂), zinc bromide (ZnBr₂) and zinc cyanide (Zn(CN)₂).Other preferred metal salts may include metal sulfates such as zincsulfate (ZnSO₄).

More particularly, the disclosed compositions may be chelatedcompositions that provide a stable micronutrient formula that is alsocompatible with soil and foliar nutrients and/or pesticide mixes. Insome implementations, the chelated compositions may include a metaloxide, citric acid and glutamic acid at a molar ratio ranging from about1:6.8:0.5 to about 1:1:0.29. In particular implementations, the chelatedcompositions may include a metal salt:citric acid:glutamic acid molarratio of about 2:14:1, 2:13:1, 2:12:1, 2:10:1, 2:9:1, 2:8:1, 2:7:1,2:6:1, 2:5:1, 2:4:1, 2:3:1, 2:2:1, 1:0.9:0.5, or 1:1:0.29. A zincoxide:citric acid:glutamic acid molar ratio of, 2:2:1, 1:0.9:0.5, or1:1:0.29 may be preferred in some implementations (e.g., with 81.4 g/molZnO: 192.1 g/mol citric acid: 147.1 g/mol glutamic acid).

According to some implementations, the compositions of the presentdisclosure may be free of other chelating agents such asethylenediaminetetraacetic acid (EDTA) and variations thereof such asits conjugate base ethylenediamine tetraacetate (e.g., tetrasodiumethylenediamine tetraacetate). Particularly, the combination of citricacid and glutamic acid is effective to bind the metal ions of themicronutrient and prevents phosphate salt from converting themicronutrients to insoluble solids without requiring the use of othercommonly known chelating agents such as EDTA. The application of theorganic acids of the present disclosure without EDTA can additionally beuseful in avoiding phytotoxicity, e.g., burning. In addition oralternatively, the chelating agents in the disclosed compositions mayconsist of or consist essentially of glutamic acid and citric acid. Suchchelating agents may be chelated with one or more metal ions and/or maybe present in the admixture in excess. Other components such as water,defoaming agents, a source of sugar, surfactants, biocides, propyleneglycol, sodium hydroxide, may be present in the disclosed compositions,for instance, as necessary components for the manufacture anddistribution of the stability and compatibility-enhancing product,without affecting the effectiveness of the chelating components.

A number of pesticides, e.g., herbicides, insecticides and/or fungicidesare compatible with the compositions of the present disclosure. Theseherbicides include but are not limited to: N-(phosphonomethyl)glycine,e.g., glyphosate, in various forms including in the form of a salt,ester or other derivative thereof. Examples of glyphosate productsinclude but are not limited to: its form as a potassium salt (e.g.,Roundup PowerMax and Touchdown Total), as a dimethylamine salt (e.g.,Durango DMA), in is form as an isopropylamine salt (e.g., Cornerstone5+), and glyphosate in combination with other pesticides such as2,4-Dichlorophenoxyacetic acid (2,4-D) (e.g., Enlist Duo) and withdicamba (e.g., Mon 76832 and Roundup Xtend).

Other compatible herbicides include, but are not limited to: the sodiumsalt of bentazon (3-(1-methylethyl)-1H-2, 1,3-benzothiadiazin-4 (3H)-one2,2,-dioxide) (e.g., Basagran); diglycolamine salt of3,6-dichloro-o-anisic acid (e.g., Sterling Blue);3,6-dichloro-2-methoxybenzoic acid (e.g., Dicamba, Enginia);2,4-Dichlorophenoxyacetic acid (2,4-D);1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine (Atrazine); amideherbicides; arsenical herbicides; carbamate and thiocarbamateherbicides; carboxylic acid herbicides; dinitroaniline herbicides;heterocyclic nitrogen-containing herbicides; organophosphate compounds;urea herbicides; and quaternary herbicides;5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamide(Fomesafen); tembotrione (e.g., Laudis).

Weeds that may be controlled using the herbicide compositions mayinclude, but are not limited to: barnyard grass, green foxtail, wildoats, nightshade, velvetleaf, annual morningglory, yellow nutsedge,pigweed, downy brome.

According to certain implementations, compatible herbicides may includenitrogen, phosphorus and potassium elements, in a ratio that allows thecomposition to function as both a herbicide and a fertilizer.Fertilizers that may be compatible with the compositions of the presentdisclosure may include but are not limited to N—P—K fertilizers such as9-18-9 and 10-34-0 fertilizers and atrazine-containing fertilizers.

In addition or alternatively, the herbicides may include insecticidesand/or fungicides. Insecticides that may be compatible with thedisclosed compositions include but are not limited to: pyrethroidinsecticides (e.g., bifenthrin); pyrethrins or other botanicals (e.g.D-limonene, linalool, ryania, rotenone, eugenol (clove oil);chloronicotinyls; essential oils (e.g., lemongrass, pepper wintergreen,rosemary, cinnamon, sesame, thyme, cedar oils and capsaicin); neem oil(e.g., Azadirachtin); nicotine; microbial products (e.g., Bacillusthuringeinis and Beauveria bassiana); oxadiazines (e.g., Indoxacarb);anthranilic diamide (e.g., chlorantraniliprole); juvenile hormone mimics(e.g., fenoxycarb; pyriproxifen; methoprene; and hydroprene), pyrroles(e.g., chlorfenapyr), phenylpyrazoles (e.g., fipronil), organophosphates(e.g., malathion and chlorpyrifos), inorganics (e.g., sulfur and dormantand horticultural oils); insect growth regulators such as chitinsynthesis inhibitors (e.g., hexaflumuron; noviflumuron; diflubenzuron;buprofezine; cyromazine; and halofenozide); acaricides such as miticides(e.g., avermectin) and ixodicides alone or in any combination with thecompositions of the present disclosure. Fungicides that may becompatible with the disclosed compositions include but are not limitedto: fluxapyroxad, pyraclostrobin, propiconazole, trifloxystrobin,prothioconazole, 1,2-propanediol, azoxystrobin (e.g. Priaxor, On Set,Topaz, Headline amp, Headline sc, Stratego, Quadris) alone or in anycombination with the compositions of the present disclosure.

In addition, fertilizers alone (e.g., not necessarily in the presence ofa pesticide) may be compatible with the compositions of the presentdisclosure and may include but are not limited to N—P—K fertilizers suchas 9-18-9 and 10-34-0 fertilizers.

The compositions of the present disclosure differ from an approachdisclosed in U.S. Pat. No. 5,504,055 (the '055 patent) in which a zincoxide/citrate/glutamate chelate was prepared by deaerating water andcombining zinc oxide, citric acid and glutamic acid at a ratio of 3:1:10by weight (i.e., a molar ratio of 1:0.16:2, with 81.4 g. zinc oxide, 30g. citric acid, 294.2 g. glutamic acid) to form an aqueous solution thatwas subsequently dried to form a zinc amino acid chelate. While thechelate of the '055 patent was described as improving plant performancewhen combined with plant nutrients over a control that does not use sucha zinc amino acid chelate, studies of this chelate show that it is notstable and therefore cannot be applied in agricultural settings.Particularly, FIGS. 1A and 1B (right side) are pictures showing a zincoxide/citrate/glutamate mixture at a molar ratio of 1:0.16:2 that wasprepared according to the method described in Example XI of the '055patent; while the left side of FIG. 1B, i.e., the container labeled AGM14032, is an image of the composition of the present disclosure at a2:2:1 ratio of zinc oxide:citric acid:glutamic acid. FIG. 1A was taken24 hours after stirring the '055 patent mixture and prior to filtration.The opaque layer is the zinc ion converted to an insoluble, white solid,and the clear layer is citric acid in water. Prolonged stirring was anattempt to cause the components to dissolve in solution. The picture ofthe '055 patent mixture in FIG. 1B was taken 24 hours after filtrationand shows an opaque mixture of precipitated solids below a clear layer.Consequently, the zinc oxide/citrate/glutamate molar ratio of 1:0.16:2does not form a stable composition. In contrast, the left side of thepicture of FIG. 1B shows the AGM 14032 mixture 24 hours after mixingwhere the citrate and glutamate has chelated with the zinc ions, whichresults in the mixture being clear orange due to the non-precipitationof the zinc in the mixture. The mixture remained in this stable,non-precipitated state for over 42 days.

Production of the Stability and Compatibility-Enhancing Composition

To produce the chelated compositions of the present disclosure, a metaloxide (e.g., zinc oxide), glutamic acid, citric acid, and an amount ofsodium hydroxide needed to raise the pH to 7.5 may be mixed with waterand agitated at about 130° F. until all raw materials are solubilizedand the mixture is clear and colorless. Water may be added to achievethe desired volume and the mixture agitated until the product ishomogenous. The metal oxide, glutamic acid, and citric acid may be addedin any order. In one implementation, the mixture may contain 7.5% zincoxide, 18.4% citric acid, and 7.1% glutamic acid (e.g., at a molar ratioof 2:2:1). The mixture of components yields an exothermic reaction andthe temperature of the mixture was monitored and maintained at atemperature below 165° F., preferably below 165° F. During production,the pH of the mixture is acidic (e.g., at a pH of about 3) and may beadjusted to about 7.5. The final pH of the product after 24 hours isabout 8.0.

The chelated compositions may be converted to a solid such aswater-soluble powders, granules and/or prills. In addition oralternatively, the compositions may be combined with micronutrients andthe chelate may be converted to a solid.

The chelated compositions of the present disclosure are stable undervarious conditions, including but not limited to: freeze/thaw conditions(−18° C. ±2° C.) for over five cycles, refrigerator conditions (0° C.±2° C.) for over three months, elevated temperatures (54° C. ±2° C.) forover five weeks, which equates to a shelf-life at room temperature ofmore than 12 months. Particularly, per ASTM protocols, a mixture that isstable under oven conditions at 54° C. for two weeks is equivalent to a12-month shelf-life at room temperature, meaning the compositions of thepresent disclosure that are stable for five weeks have a shelf life thatexceeds 12 months.

In addition, the chelated compositions of the present disclosure arecompatible with the disclosed pesticides including but not limited to:glyphosate, 2,4-D, Sterling Blue, Basagran, Atrazine, Enginia, Enlistduo and derivatives thereof. Particularly, mixtures of the disclosedcompositions and the pesticides do not exhibit flocculation, sludge,gelling, clumping, precipitation, separation, or non-dispersible oilover common test periods such as 15 minutes, 2 hours, 6 hours or 24hours or extended periods of time, such as 72 hours, or at least one,two, three, four, five or six weeks.

Methods of use: The disclosed compositions may be applied inagricultural spray applications such as to seed, soil, foliage andfruit. Such sprays may be delivered using ground and aerialapplications.

Prior to use, the disclosed compositions may be mixed with, forinstance, water, micronutrients, pesticides, antimicrobial compositions,defoamers, adjuvants (e.g., alkyl polyglycosides), monosaccharaides(e.g., high fructose corn syrup), disaccharides, formulation aids (e.g.,propylene glycol), surfactants (e.g., cationic, anionic and/or nonionic)and pH adjusters. Mixing may be conducted under agitation and may takeplace at ambient temperatures, e.g., about 70 to 90° F. depending onclimate, or may take place under elevated temperatures above 90° F. Thestability and compatibility-enhancing compositions (e.g., chelatedcompositions) may have a pH of about 8.0 prior to mixing.

The compositions of the present disclosure perform similarly or betterthan chelated products containing EDTA with respect to micronutrientuptake by the plant without causing phytotoxicity. The compositionsadditionally provide benefits over the use of EDTA due to environmentalfate questions in connection with its use.

Examples

Stability

A stability and compatibility-enhancing composition of zinc oxide,citric acid and glutamic acid at a molar ratio of 2:2:1 was subjected tostability testing using a procedure modified from CIPAC MT 39 and CIPACMT 46.3, and involved freeze/thaw, refrigerator, and oven stabilitytesting.

Materials and Methods: The apparatuses used in the stability testingincluded: a graduated jar, 120 mL; a flashlight; an oven, controlled toa specified temperature (±2° C.); and a refrigerator/freezer controlledto a specified temperature (±2° C.).

The freeze/thaw stability testing procedure involved transferring anamount of product into a graduated jar; placing the jar into the freezerat −18° C. ±2° C.; after 24 hours, the sample was taken out of thefreezer and allowed to come to room temperature; upon reaching roomtemperature, the product had undergone one cycle. The sample wassubjected to five (5) total cycles.

Freeze/thaw evaluation was conducted after each cycle and observationswere taken for any disruption in product formulation including but notlimited to, phasing, creaming, settling, crystal growth, precipitation,changes in color, and/or discoloration of container. A flashlight wasused to observe darker formulations. If changes in formulation werenoticed, numbers of inversions required to get product homogenous was berecorded. If inversion of the product did not homogenize product, thetest was considered a fail.

Using refrigeration to test stability involved transferring product intoa graduated jar; placing the jar into a refrigerator at 0° C. ±2° C.;and checking for any change every day for four weeks. After the fourweek period, the product was checked once a week. The product was testedfor three months.

Stability evaluation for refrigeration was conducted each time theproduct was checked, and observations were taken and recorded accordingthe method described in connection with the freeze/thaw evaluation.

Testing stability under elevated temperatures involved using an oven. Anamount of product was transferred into a graduated jar and placed intoan oven at 54° C. ±2° C. The product was checked for any change everyday for four weeks. After four weeks, the product was checked once aweek. The product was allowed to stay in the oven for 3 months.

Stability evaluation under elevated temperature was conducted each timethe product was checked, and observations were taken and recordedaccording the method described in connection with the freeze/thawevaluation.

Results: The results of the stability testing showed the composition wasstable under freeze/thaw conditions for over five cycles; was stable inrefrigerator conditions for over three months; and was stable under heatfor over five weeks, which equates to a shelf-life of more than 12months.

Compatibility

The stability and compatibility-enhancing composition containing zincoxide, citric acid and glutamic acid at a molar ratio of 2:2:1 wastested for compatibility with pesticides using a modified approach fromASTM E1518-05(2012), Standard Practice for Evaluation of PhysicalCompatibility of Pesticides in Aqueous Tank Mixtures by the DynamicShaker Method, ASTM International, West Conshohocken, Pa., 2012. Thepesticides tested included: glyphosate including in its various formsincluding Roundup Power Max, Durango, Cornerstone 5+, Touchdown Total;2,4-D; Sterling Blue; Basagran; Atrazine; Enginia; Enlist duo andRoundup Xtend.

Materials and Methods: The apparatuses used in compatibility testingincluded: 1. a graduated cylinder, 120 mL; 2. transfer pipets; 3.balance, ±0.01 g; 4. a sieve, U.S. standard, 50 mesh (300 μm), 3 inchesin diameter; and 5. a flashlight. With respect to the reagents used,reagent grade chemicals were used in all tests and the water had apurity level of Type IV. Synthetic water was made according to CIPAChandbook F section MT18.

The final disposition of the compatibility test was on or around 100 mL,and the ratios needed to bring an application of 10 gallons per acre to100 mL per acre were calculated. 70 percent of the water needed for thecompatibility test was added to the cylinder at room temperature. Theremaining components were added for the jar test according to WALES andDALES unless otherwise specified by the product label. Applicationsrates were used from the product label. The liquid products weredelivered using the transfer pipet or weigh in solid products. Aftereach individual product had been added, the jar was capped and swirledby hand until the product became homogenous. After all of the productwater had been added, the remaining the water was be added. The entiremix was agitated for a period of no less than 30 seconds.

Testing and evaluations were conducted 0.25, 2, 6, 24, and 72 hoursafter agitating the mixture. Evaluations were separated into sevencategories that are flocculation, sludge, gelling, clumping,precipitation, separation, and non-dispersible oil. A grading of 1-5 wasused for each category (1 being the presence of none, 5 having thehighest presence).

Results: The results of the compatibility testing showed the compositiondid not have any flocculation, sludge, gelling, clumping, precipitation,separation, or non-dispersible oil after 42 days. All categories foreach of the herbicides tested scored a 1 over this time period.

Uptake/Efficiency

This zinc foliar uptake trial was conducted at River Falls, Wis. andRosemount, Minn. during the 2015 corn growing season. The trial was laidout on a randomized-complete block design with four replications. Plotsize was 10 feet by 30 feet. An equivalent amount of zinc, 0.11lb./acre, was applied foliarly to corn at a 10 gallon/acre totalapplication rate to each plot utilizing four different products withanalysis in parenthesis: a stability and compatibility-enhancingcomposition of the present disclosure (0-0-0-6.0Zn) containingZnO/citric acid/glutamic acid at molar ratio of 1:1:0.5; Ultra-Che Zinc9% EDTA (7-0-0-9Zn) (derived from zinc diammoniumethylenediaminetetracetate (EDTA)); and Citri-Che Zinc 10% (6-0-0-10Zn)(derived from: zinc chloride, zinc oxide, zinc EDTA, citric acid andammonium hydroxide). All products tested were chelated. The compositionof the present disclosure was free of EDTA and its derivatives, whilethe two compositions tested contained chelated EDTA.

Prior to the foliar application of the zinc-containing products, acomposite tissue sample, comprised of the uppermost, fully developedcorn leaf, was collected from across the trial area. This sampleestablished the pre-existing zinc content of the corn plants.

Zinc uptake from a foliar application of the disclosed compositionapplied to corn at the V4 growth stage was measured by plant tissueanalysis. A plant tissue sample was collected from each plot six dayspost-application. The sample was the uppermost, fully developed cornleaf taken from every plant from the center two rows of the plot. Thecenter two rows were the only rows utilized to ensure the plants sampledreceived even coverage during product application and to eliminate thepotential for spray-overlap. The corn tissue was analyzed by MidwestLaboratories (13611 B Street, Omaha, Nebr. 68144).

Results: The results of Table 1 illustrate that the disclosedcomposition of the present disclosure performs similarly or better thanthe chelated products containing EDTA.

TABLE 1 Average % Corn Tissue % Zinc Product Zinc Rate Zinc (ppm)Increase Untreated Check — 31 — Glutamic acid/citric acid 6% 20.7 fl.oz./acre 34.25 10.5% chelated with zinc (from ZnO) Ultra-Che Zinc 9%(with 9%   14 fl. oz./acre 32.75  6.5% EDTA) Citri-Che Zinc 10% 10% 13.5 fl. oz./acre 35 12.9% (with EDTA)

While methods disclosed herein have been described and shown withreference to particular operations performed in a particular order, itwill be understood that these operations may be combined, sub-divided,or re-ordered to form equivalent methods without departing from theteachings of the present disclosure. Accordingly, unless specificallyindicated herein, the order and grouping of the operations should not beconstrued as limiting.

Similarly, it should be appreciated that in the foregoing description ofexample embodiments, various features are sometimes grouped together ina single embodiment or description thereof for the purpose ofstreamlining the disclosure and aiding in the understanding of one ormore of the various aspects. These methods of disclosure, however, arenot to be interpreted as reflecting an intention that the claims requiremore features than are expressly recited in each claim. Rather, as thefollowing claims reflect, inventive aspects lie in less than allfeatures of a single foregoing disclosed embodiment, and each embodimentdescribed herein may contain more than one inventive feature.

While the present disclosure has been particularly shown and describedwith reference to embodiments thereof, it will be understood by thoseskilled in the art that various other changes in the form and detailsmay be made without departing from the spirit and scope of thedisclosure.

What is claimed is:
 1. A method of spraying an agricultural admixture,comprising: spraying an admixture comprising citric acid, glutamic acid,a metal salt and one or more agricultural chemicals, the metal saltcomprising one or more zinc, boron, copper, iron, chloride, manganese,molybdenum, cobalt, magnesium, calcium, nickel, vanadium, or chromium;wherein the citric acid, glutamic acid and metal salt form a chelate tothereby prevent the metal salt from forming an insoluble solid with theone or more agricultural chemicals, and wherein the citric acid and theglutamic acid are present in the agricultural spray at a molar ratio ofabout 14:1 to about 0.9:0.5, wherein the admixture is a liquid thatremains stable, non-precipitated for at least 72 hours.
 2. The method ofclaim 1, wherein the one or more agricultural chemicals includes atleast one of: one or more pesticides; one or more fertilizers; or one ormore additional agricultural chemicals containing a component capable ofprecipitating with the metal salt in the absence of the citric acid andthe glutamic acid.
 3. The method of claim 1, wherein the citric acid andthe glutamic acid are present in the agricultural spray at a molar ratioof about 6.8:0.5 to about 1:0.29.
 4. The method of claim 1, wherein themetal salt is present with the citric acid and the glutamic acid at amolar ratio of about 2:14:1 to about 1:0.9:0.5.
 5. The method of claim1, wherein the metal salt is present with the citric acid and glutamicacid at a molar ratio of about 2:2:1, about 1:0.9:0.5, or about1:1:0.29.
 6. The method of claim 1, wherein the admixture does notexhibit at least one of flocculation, sludge, gelling, clumping,precipitation, separation, or non-dispersible oil over at least oneweek.
 7. The method of claim 1, further comprising admixing the citricacid, glutamic acid, and the metal salt.
 8. A method of producing anagricultural spray, comprising: admixing citric acid, glutamic acid, ametal salt and one or more agricultural chemicals, the metal saltcomprising one or more of zinc, boron, copper, iron, chloride,manganese, molybdenum, cobalt, magnesium, calcium, nickel, vanadium, orchromium; wherein the citric acid and the glutamic acid are admixed at amolar ratio of about 14:1 to about 0.9:0.5; wherein the citric acid,glutamic acid and metal salt form a chelate; and wherein theagricultural spray is a liquid that remains stable, non-precipitatedover 72 hours.
 9. The method of claim 8, wherein the one or moreagricultural chemicals include at least one of: one or more pesticides;one or more fertilizers; or one or more additional agriculturalchemicals containing a component capable of precipitating with the metalsalt in the absence of the citric acid and the glutamic acid.
 10. Themethod of claim 8, wherein the one or more agricultural chemicalscomprise one or more pesticides, the one or more pesticides comprisingone or more of: N-(phosphonomethyl)glycine, 4-Dichlorophenoxyaceticacid, bentazon, 3,6-dichloro-o-anisic acid,3,6-dichloro-2-methoxybenzoic acid,1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine, amide herbicides,arsenical herbicides, carbamate and thiocarbamate herbicides, carboxylicacid herbicides, dinitroaniline herbicides, heterocyclicnitrogen-containing herbicides, organophosphate compounds, ureaherbicides, and quaternary herbicides,5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamide,tembotrione or an ester of the pesticide.
 11. The method of claim 8,wherein the metal salt includes a metal oxide.
 12. The method of claim8, wherein the agricultural spray does not exhibit at least one offlocculation, sludge, gelling, clumping, precipitation, separation, ornon-dispersible oil over at least one week.
 13. The method of claim 8,wherein the agricultural spray remains stable, non-precipitated for atleast 42 days.
 14. The method of claim 8, further comprising providing acomposition including the citric acid and glutamic acid with a metalsalt; and wherein, after providing the composition, admixing citric acidand glutamic acid with a metal salt and one or more agriculturalchemicals includes admixing the composition with the one or moreagricultural chemicals.
 15. The method of claim 14, wherein providingthe composition includes admixing the citric acid, glutamic acid, andthe metal salt.
 16. An agricultural spray, comprising: a metal salt,citric acid and glutamic acid in a molar ratio of about 2:14:1 to about1:0.9:0.5, the metal salt comprising one or more of zinc, boron, copper,iron, chloride, manganese, molybdenum, cobalt, magnesium, calcium, ornickel, vanadium, or chromium; wherein the citric acid, glutamic acidand metal salt form a chelate; and one or more agricultural chemicals;wherein the agricultural spray is a liquid that remains stable,non-precipitated for at least 72 hours.
 17. The agricultural spray ofclaim 16, wherein the admixture includes at least one of: one or morepesticides; one or more fertilizers; or one or more additionalagricultural chemicals containing a component capable of precipitatingwith the metal salt in the absence of the citric acid and the glutamicacid.
 18. The agricultural spray of claim 16, wherein the one or moreagricultural chemicals comprise one or more pesticides, the one or morepesticides comprising one or more of: N-(phosphonomethyl)glycine,4-Dichlorophenoxyacetic acid, bentazon, 3,6-dichloro-o-anisic acid,3,6-dichloro-2-methoxybenzoic acid,1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine, amide herbicides,arsenical herbicides, carbamate and thiocarbamate herbicides, carboxylicacid herbicides, dinitroaniline herbicides, heterocyclicnitrogen-containing herbicides, organophosphate compounds, ureaherbicides, and quaternary herbicides,5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamide,tembotrione or an ester of the pesticide.
 19. The agricultural spray ofclaim 16, wherein the agricultural spray does not exhibit at least oneof flocculation, sludge, gelling, clumping, precipitation, separation,or non-dispersible oil over at least one week.
 20. The agriculturalspray of claim 16, wherein the agricultural spray remains stable,non-precipitated for at least 42 days.